This dissertation is divided into three major sections (one on dendrimers, one on tripodal metal ligands and one on a research oriented chemistry curricula) with a primary focus on different types of multicomponent assemblies. In the first chapter, a system is described that used a multicomponent assembly of AT-PAMAM dendrimers and an indicator, carboxyfluorescein, to detect and identify various polyanions at a low micromolar concentration. The system was able to successfully differentiate twelve anions, many of biological interest, including three tricarboxylates. The tricarboxylates were differentiated based primarily on the regiochemistry of the anionic groups. In the second chapter, further studies with AT-PAMAM dendrimers were carried out to provide some understanding of the thermodynamic origins of binding. Utilizing isothermal titration calorimetry, the binding of the dendrimers to large polyanionic dendrons with increasing numbers of charges was studied. Through these studies, the thermodynamic values of the binding events were obtained allowing us to explore the properties of the dendrimers. The cooperativity of the system was measured, and primarily negative cooperativity determined by the entropic contributions was uncovered. As the dendrimers increased in size, the thermodynamic origins of binding were determined to a greater extent by the entropy of binding. In the third chapter, a novel dynamic ligand system for metal binding is described. In the presence of a metal salt, a heterocyclic aldehyde and a secondary amine with two heterocyclic arms reversibly condense to form a hemiaminal with a tripodal metal binding site. This chapter describes studies on the metal binding ability, the variety of metals that will lead to this formation, the effects of anions and the range of aldehydes that can be used are described. Furthermore, the system’s reversibility was explored. Finally, the use of a bistriazole secondary amine was explored. The modular nature of triazole formation could lead to the introduction of additional functionalities. The fourth chapter discusses how the novel ligand system could be used to study the enantiomeric excess (ee) of chiral thiols. Based upon the system’s ability to form a stable hemiaminal thioether, a CD signal could be generated that is proportional to the amount of a particular enantiomer in solution. Using this system, a calibration curve relating CD signal and ee can be generated giving the ee of an unknown solution. In the final chapter, a look at the Freshman Research Initiative will be carried out with a focus on the ability to teach basic skills in an introductory laboratory through research. Four different skills or techniques will be explored through three different FRI streams,x and how they teach the four skills. Finally, analysis of the success of the program, particularly students’ success in the next laboratory course in the sequence, is discussed, and a model for adopting this type of teaching at other universities is given. / text

In the past 30 years, the discovery of capabilities of nucleic acids far beyond their well-known information-bearing capacity has profoundly influenced our understanding of these polymers. The discovery by the Cech and Altman labs that nucleic acids could perform catalytic functions, coupled with the Gold and Szostak groups’ demonstration of the de novo evolution of nucleic acids that bind arbitrary ligands, has resulted in a proliferation of newfound roles for these molecules. Nucleic acids have found utility in both engineered systems, such as aptamer therapeutics, as well as in newly appreciated roles in extant organisms, such as riboswitches. As a result of these discoveries, many have pondered the potential importance of the dual (catalytic and informational) roles of nucleic acids in early evolution. A high-yielding synthetic route for the nonenzymatic polymerization of nucleic acids, based on the aqueous self-assembly of their components, would provide a powerful tool in nucleic acid chemistry, with potential utility in prebiotic and contemporary nucleic acid systems alike – however, such a route remains elusive. In this thesis, I describe several steps towards such a synthetic route. In these systems, a nucleic-acid binding ligand drives the assembly of short DNA and RNA duplexes, promoting the production of long nucleic acid polymers, while suppressing the production of short, cyclic species. Additionally, the use of a reversible covalent linkage allows for the production of long polymers, as well as the incorporation of previously cyclized products into these polymers. I also report several explorations of novel base pairings, nucleic acid-ligand interactions, and nucleic acid-ion interactions that have informed our studies of self-assembling nucleic acid systems.